This invention relates to methods of oxidizing hydrocarbons, such as cyclohexane for example, to respective dibasic acids, such as adipic acid for example, and more specifically, how to remove catalyst after the reaction, preferably for recycling, and how to treat the remaining mixture after removing the catalyst.
There is a plethora of references (both patents and literature articles) dealing with the formation of acids, one of the most important being adipic acid, by oxidation of hydrocarbons. Adipic acid is used to produce Nylon 66 fibers and resins, polyesters, polyurethanes, and miscellaneous other compounds.
There are different processes of manufacturing adipic acid. The conventional process involves a first step of oxidizing cyclohexane with oxygen to a mixture of cyclohexanone and cyclohexanol (KA mixture), and then oxidation of the KA mixture with nitric acid to adipic acid. Other processes include, among others, the xe2x80x9cHydroperoxide Process,xe2x80x9d the xe2x80x9cBoric Acid Process,xe2x80x9d and the xe2x80x9cDirect Synthesis Process,xe2x80x9d which involves direct oxidation of cyclohexane to adipic acid with oxygen in the presence of solvents, catalysts, and promoters.
The Direct Synthesis Process has been given attention for a long time. However, to this date it has found little commercial success. One of the reasons is that although it looks very simple at first glance, it is extremely complex in reality. Due to this complexity, one can find strikingly conflicting results, comments, and views in different references.
It is well known that after a reaction has taken place according to the Direct Synthesis, a mixture of two liquid phases is present at ambient temperature, along with a solid phase mainly consisting of adipic acid. The two liquid phases have been called the xe2x80x9cPolar Phasexe2x80x9d and the xe2x80x9cNon-Polar Phasexe2x80x9d. However, no attention has been paid so far to the importance of the two phases, except for separating the adipic from the xe2x80x9cPolar Phasexe2x80x9d and recycling these phases to the reactor partially or totally with or without further treatment.
It is also important to note that most studies on the Direct Synthesis-have been conducted in a batch mode, literally or for all practical purposes.
As aforementioned, there is a plethora of references dealing with oxidation of organic compounds to produce acids, such as, for example, adipic acid and/or intermediate products, such as for example cyclohexanone, cyclohexanol, cyclohexylhydroperoxide, etc.
The following references, among others, may be considered as representative of oxidation processes relative to the preparation of diacids and other intermediate oxidation products.
U.S. Pat. No. 5,463,119 (Kollar) discloses a process for the oxidative preparation of C5-C8 aliphatic dibasic acids by
(1) reacting,
(a) at least one saturated cycloaliphatic hydrocarbon having from 5 to 8 ring carbon atoms in the liquid phase and
(b) an excess of oxygen gas or an oxygen-containing gas in the presence of
(c) a solvent comprising an organic acid containing only primary and/or secondary hydrogen atoms and
(d) at least about 0.002 mole per 1000 grams of reaction mixture of a polyvalent heavy metal catalyst;
(2) removing the aliphatic dibasic acid; and
(3) recycling intermediates, post oxidation components, and derivatives thereof remaining after removal of the aliphatic dibasic acid into the oxidation reaction.
U.S. Pat. No. 5,374,767 (Drinkard et al.) discloses formation of cyclohexyladipates in a staged reactor, e.g., a reactive distillation column. A mixture containing a major amount of benzene and a minor amount of cyclohexene is fed to the lower portion of the reaction zone and adipic acid is fed to the upper portion of the reaction zone, cyclohexyladipates are formed and removed from the lower portion of the reaction zone and benzene is removed from the upper portion of the reaction zone. The reaction zone also contains an acid catalyst.
U.S. Pat. No. 5,321,157 (Kollar) discloses a process for the preparation of C5-C8 aliphatic dibasic acids through oxidation of corresponding saturated cycloaliphatic hydrocarbons by
(1) reacting, at a cycloaliphatic hydrocarbon conversion level of between about 7% and about 30%,
(a) at least one saturated cycloaliphatic hydrocarbon having from 5 to 8 ring carbon atoms in the liquid phase and
(b) an excess of oxygen gas or an oxygen containing gas mixture in the presence of
(c) less than 1.5 moles of a solvent per mole of cycloaliphatic hydrocarbon (a), wherein said solvent comprises an organic acid containing only primary and/or secondary hydrogen atoms and
(d) at least about 0.002 mole per 1000 grams of reaction mixture of a polyvalent heavy metal catalyst; and
(2) isolating the C5-C8 aliphatic dibasic acid.
U.S. Pat. No. 3,987,100 (Barnette et al.) describes a process of oxidizing cyclohexane to produce cyclohexanone and cyclohexanol, said process comprising contacting a stream of liquid cyclohexane with oxygen in each of at least three successive oxidation stages by introducing into each stage a mixture of gases comprising molecular oxygen and an inert gas.
U.S. Pat. No. 4,680,098 (Chang) describes an electrodialysis method for recovering cobalt or cobalt and manganese from a solution containing oxygenated aromatic compounds.
U.S. Pat. No. 3,957,876 (Rapoport et al.) describes a process for the preparation of cyclohexyl hydroperoxide substantially free of other peroxides by oxidation of cyclohexane containing a cyclohexane soluble cobalt salt in a zoned oxidation process in which an oxygen containing gas is fed to each zone in the oxidation section in an amount in excess of that which will react under the conditions of that zone.
U.S. Pat. No. 3,932,513 (Russell) discloses the oxidation of cyclohexane with molecular oxygen in a series of reaction zones, with vaporization of cyclohexane from the last reactor effluent and parallel distribution of this cyclohexane vapor among the series of reaction zones.
U.S. Pat. No. 3,530,185 (Pugi) discloses a process for manufacturing precursors of adipic acid by oxidation with an oxygen-containing inert gas which process is conducted in at least three successive oxidation stages by passing a stream of liquid cyclohexane maintained at a temperature in the range of 140xc2x0 to 200xc2x0 C. and a pressure in the range of 50 to 350 p.s.i.g. through each successive oxidation stage and by introducing a mixture of gases containing oxygen in each oxidation stage in an amount such that substantially all of the oxygen introduced into each stage is consumed in that stage thereafter causing the residual inert gases to pass countercurrent into the stream of liquid during the passage of the stream through said stages.
U.S. Pat. No. 3,515,751 (Oberster et al.) discloses a process for the production of epsilon-hydroxycaproic acid in which cyclohexane is oxidized by liquid phase air oxidation in the presence of a catalytic amount of a lower aliphatic carboxylic acid and a catalytic amount of a peroxide under certain reaction conditions so that most of the oxidation products are found in a second, heavy liquid layer, and are directed to the production of epsilon-hydroxycaproic acid.
U.S. Pat. No. 3,361,806 (Lidov et al.) discloses a process for the production of adipic acid by the further oxidation of the products of oxidation of cyclohexane after separation of cyclohexane from the oxidation mixture, and more particularly to stage wise oxidation of the cyclohexane to give high yields of adipic acid precursors and also to provide a low enough concentration of oxygen in the vent gas so that the latter is not a combustible mixture.
U.S. Pat. No. 3,234,271 (Barker et al.) discloses a process for the production of adipic acid by the two-step oxidation of cyclohexane with oxygen. In a preferred embodiment, mixtures comprising cyclohexanone and cyclohexanol are oxidized. In another embodiment, the process involves the production of adipic acid from cyclohexane by oxidation thereof, separation of cyclohexane from the oxidation mixture and recycle thereof, and further oxidation of the other products of oxidation.
U.S. Pat. No. 3,231,608 (Kollar) discloses a process for the preparation of aliphatic dibasic acids from saturated cyclic hydrocarbons having from 4 to 8 cyclic carbon atoms per molecule in the presence of a solvent which comprises an aliphatic monobasic acid which contains only primary and secondary hydrogen atoms and a catalyst comprising a cobalt salt of an organic acid, and in which process the molar ratio of said solvent to said saturated cyclic hydrocarbon is between 1.5:1 and 7:1, and in which process the molar ratio of said catalyst to said saturated cyclic hydrocarbon is at least 5 millimoles per mole.
U.S. Pat. No. 3,161,603 (Leyshon et al.) discloses a process for recovering the copper-vanadium catalyst from the waste liquors obtained in the manufacture of adipic acid by the nitric acid oxidation of cyclohexanol and/or cyclohexanone.
U.S. Pat. No. 2,565,087 (Porter et al.) discloses the oxidation of cycloaliphatic hydrocarbons in the liquid phase with a gas containing molecular oxygen and in the presence of about 10% water to produce two phases and avoid formation of esters.
U.S. Pat. No. 2,557,282 (Hamblet et al.) discloses production of adipic acid and related aliphatic dibasic acids; more particularly to the production of adipic acid by the direct oxidation of cyclohexane.
U.S. Pat. No. 2,439,513 (Hamblet et al.) discloses the production of adipic acid and related aliphatic dibasic acids and more particularly to the production of adipic acid by the oxidation of cyclohexane.
U.S. Pat. No. 2,223,494 (Loder et al.) discloses the oxidation of cyclic saturated hydrocarbons and more particularly to the production of cyclic alcohols and cyclic ketones by oxidation of cyclic saturated hydrocarbons with an oxygen-containing gas.
U.S. Pat. No. 2,223,493 (Loder et al.) discloses the production of aliphatic dibasic acids and more particularly to the production of aliphatic dibasic acids by oxidation of cyclic saturated hydrocarbons with an oxygen-containing gas.
German Patent DE 44 26 132 A1 (Kysela et al.) discloses a method of dehydration of process acetic acid from liquid-phase oxidation of cyclohexane with air, in the presence of cobalt salts as a catalyst after separation of the adipic acid after filtration, while simultaneously avoiding cobalt salt precipitates in the dehydration column, characterized in that the acetic acid phase to be returned to the beginning of the process is subjected to azeotropic distillation by the use of added cyclohexane, under distillative removal of the water down to a residual content of less than [sic] 0.3-0.7%.
Patent EP 646 107 A1 (Habermann et al.) discloses a method of producing dicarboxylic acids and diamines by cleavage, with a base, of polymers produced by the dicarboxylic acids and the diamines. The method involves a later step of electrodialysis, in which the dicarboxylic acids are separated and the base formed is recycled.
PCT International Publication WO 96/03365 (Constantini et al.) discloses a process for recycling a cobalt-containing catalyst in a direct reaction of oxidation of cyclohexane into adipic acid, characterized by including a step in which the reaction mixture obtained by oxidation into adipic acid is treated by extraction of at least a portion of the glutaric acid and the succinic acid formed during the reaction.
The patent literature is inconsistent and at least confusing regarding addition or removal of water in oxidations. For example:
U.S. Pat. No. 5,221,800 (Park et al.) discloses a process for the manufacture of adipic acid. In this process, cyclohexane is oxidized in an aliphatic monobasic acid solvent in the presence of a soluble cobalt salt wherein water is continuously or intermittently added to the reaction system after the initiation of oxidation of cyclohexane as indicated by a suitable means of detection, and wherein the reaction is conducted at a temperature of about 50xc2x0 C. to about 150xc2x0 C. at an oxygen partial pressure of about 50 to 420 pounds per square inch absolute.
U.S. Pat. No. 4,263,453 (Schultz et al.) discloses a process claiming improved yields by the addition of water at the beginning of the reaction, generally of the order of 0.5 to 15% relative to monobasic aliphatic acid solvent, and preferably 1 to 10% relative to the solvent.
U.S. Pat. No. 3,390,174 (Schultz et al.) discloses a process claiming improved yields of aliphatic dibasic acids when oxidizing the respective cyclic hydrocarbons at temperatures between 130xc2x0 and 160xc2x0 C., while removing the water of reaction substantially as quickly as it is formed.
None of the above references, or any other references known to the inventors disclose, suggest or imply, singly or in combination, control of oxidation reactions by treating the reaction mixture subject to the intricate and critical controls and requirements of the instant invention as described and claimed.
Our U.S. Pat. Nos. 5,654,475, 5,580,531, 5,558,842, 5,502,245, and applications Ser. No. 08/477,195, filed on Jun. 7, 1995 U.S. Pat. No. 5,801,282; and Ser. No. 08/587,967, filed on Jan. 17, 1996 U.S. Pat. No. 5,883,292, all of which are incorporated herein by reference, describe methods and apparatuses relative to controlling reactions in atomized liquids. In addition, the following U.S. applications are also incorporated herein by reference: Ser. No. 08/812,847, filed on Mar. 6, 1997 U.S. Pat. No. 6,288,270; Ser. No. 08/824,992, filed on Mar. 27, 1997 U.S. Pat. No. 5,922,908; Ser. No. 08/859,985 filed on May 21, 1997 U.S. Pat. No. 5,801,273; Ser. No. 08/861,281 filed on May 21, 1997 now abandoned; Ser. No. 08/861,180 filed on May 21, 1997 U.S. Pat. No. 6,103,933; Ser. No. 08/861,176 filed on May 21, 1997 U.S. Pat. No. 5,824,819; Ser. No. 08/859,890 filed on May 21, 1997 U.S. Pat. No. 5,747,233; Ser. No. 08/861,210 filed on May 21, 1997 now abandoned; Ser. No. 08/876,692, filed on Jun. 16, 1997 pending; Ser. No. 08/900,323, filed on Jul. 25, 1997 U.S. Pat. No. 6,037,491; Ser. No. 08/931,035, filed on Sep. 16, 1997 now abandoned; Ser. No. 08/932,875 filed on Sep. 18, 1997 U.S. Pat. No. 6,039,902; Ser. No. 08/934,253, filed on Sep. 19, 1997 U.S. Pat. No. 5,929,277; Ser. No. 08/986,505, filed on Dec. 8, 1997 U.S. Pat. No. 5,908,589; Ser. No. 08/989,910, filed on Dec. 12, 1997 pending; Ser. No. 60/074,068, filed on Feb. 9, 1998; Ser. No. 60/075,257, filed Feb. 19, 1998; Ser. No. 60/086,159, filed May 20, 1998; Ser. No. 60/086,119, filed May 20, 1998; Ser. No. 60/086,118, filed May 20, 1998; and Ser. No. 60/091,483 filed on Jul. 2, 1998, titled xe2x80x9cMethods of Recovering Catalyst in Solution in the Oxidation of Cyclohexane to Adipic Acid.xe2x80x9d
PCT patent application PCT/US97/10830, filed on Jun. 23, 1997 of Mark W. Dassel, David C. DeCoster, Ader M. Rostami, Eustathios Vassiliou, and Sharon M. Aldrich, titled xe2x80x9cMethods and Devices for Oxidizing a Hydrocarbon to Form an Acidxe2x80x9d is incorporated herein by reference.
Also, PCT patent application PCT/US97/12944, filed on Jun. 23, 1997, of David C. DeCoster, Eustathios Vassiliou, Mark W. Dassel, Sharon M. Aldrich, and Ader M. Rostami, titled xe2x80x9cMethods and Devices for Controlling the Reaction Rate and/or Reactivity of Hydrocarbon to an Intermediate Oxidation Product by Adjusting the Oxidant Consumption Ratexe2x80x9d is incorporated herein by reference.
As aforementioned, this invention relates to methods of oxidizing hydrocarbons, such as cyclohexane for example, to dibasic acids, such as adipic acid for example, and more specifically, how to remove catalyst after the reaction, preferably for recycling. More particularly, this invention pertains a method of treating a reaction mixture produced by direct oxidation of hydrocarbon to a respective dibasic acid in a reaction zone, the reaction mixture comprising a monobasic acid solvent having only primary and/or secondary hydrogen atoms, water; and a catalyst, the method being characterized by steps of:
(a) removing a major part of the dibasic acid and a major part of the monobasic acid solvent from the reaction mixture;
(b) adding a base and optionally water into the reaction mixture after it has been treated according to step (a), thus precipitating the hydroxide of the catalyst and forming a salt with any acids present; and
(c) removing the hydroxide of the catalyst.
The method may also comprise a step of freeing the acid from the salt by electrodialysis, preferably after hydrolyzing the treated mixture after step (b) or (c). The base used for the hydrolysis may be provided at least partially by the electrodialysis step.
This invention is particularly applicable in the case that the hydrocarbon comprises cyclohexane, the dibasic acid comprises adipic acid, the monobasic acid solvent comprises acetic acid, the catalyst comprises a cobalt compound, and the base is selected from a group consisting of alkali metal hydroxide, alkaline earth hydroxide, and a mixture thereof. More preferably, the base comprises sodium hydroxide.
The oxygen formed during the electrodialysis may be used as an oxidant for the hydrocarbon, and/or the hydrogen formed during the electrodialysis may be used for energy generation.
Preferably, the catalyst hydroxide is recycled to the reaction zone either directly or after being treated, preferably in a manner to form a solution for easier handling. One type of treatment is by reacting the metal hydroxide, such as cobalt hydroxide with acetic acid to form cobalt acetate.
The method of this invention may further comprise a step of reacting the dibasic acid with a reactant selected from a group consisting of a polyol, a polyamine, and a polyamide in a manner to form a polymer of a polyester, or a polyamide, or a (polyimide and/or polyamideimide), respectively. The polymer may be further spun into fibers. Fillers or other additives may be combined with the polymer or fiber, to form composites.
All ratios and percentages are expressed by weight unless otherwise specified.
A controller, preferably a computerized controller, may handle with ease and accuracy either type of xe2x80x9clevel.xe2x80x9d Programming a computerized controller to perform such functions is a routine process, well known to the art. According to this invention, a controller, based on information received, from a reaction zone for example, controls feed rates, temperatures, pressures, and other parameters in order to achieve the desirable results. The controller may also be programmed, by techniques well known to the art, to include flow sheet simulation, which may account for vapor/liquid equilibrium and energy balance effects.
As aforementioned, these methods and devices are particularly suited in case that the hydrocarbon comprises cyclohexane, the mixture comprises acetic acid, and the catalyst comprises a cobalt salt.